1. Field of the Invention
The invention relates to new 1-aryl-5-(substituted N-cinnamylideneimino)pyrazoles and to processes for their preparation. The invention further pertains to compositions of said compounds and methods, using said compounds, for the control of arthropod, nematode, helminth or protozoan pests. In particular it relates to the application of said compounds or compositions in agricultural methods of use, particularly as pesticides, for controlling arthropods, especially insects via ingestion or contact action.
2. Description of the Related Art
Various 1-(substituted phenyl or pyridyl)-5-(substituted amino) pyrazole compounds are known to exhibit a number of different types of pesticidal activity, including activity as herbicides, plant growth regulators, insecticides, and nematicides. Included among these are the following:
U.S. Pat. No. 4,863,937 discloses as insecticides, acaricides and nematicides 1-aryl-5-(substituted N-cinnamylideneimino)pyrazoles, which are unsubstituted or alkyl or haloalkyl substituted in the 3-position of the pyrazole ring; PA1 U.S. Pat. No. 4,685,957 discloses 1-aryl-5-(substituted iminoamino)pyrazoles as herbicides and plant growth regulators, which compounds are unsubstituted or alkyl substituted in the 3-position of the pyrazole ring; PA1 EP 295,117; WO 87/03781 (also corresponding to EP 234,119); EP 295,118; and EP 350,311 disclose 1-phenyl-5-(substituted amino)pyrazole compounds for control of arthropod, nematode, helminth and protozoan pests; PA1 EP 511,845 discloses 1-aryl-5-(substituted alkylideneimino)pyrazoles for control of arthropods, nematodes, helminths, or protozoa. PA1 GB 2,136,427 discloses as herbicides 1-(substituted-2-pyridyl)-5-(substituted amino)-4-cyanopyrazoles, which are unsubstituted at the 3-position of the pyrazole ring; PA1 U.S. Pat. No. 4,772,312 discloses as herbicides 1-(substituted-2-pyridyl)-5-(substituted amino)pyrazoles, which are unsubstituted or alkyl substituted in the 3-position of the pyrazole ring; PA1 U.S. Pat. No. 4,804,675 discloses as insecticides, acaricides, and nematicides 1-(substituted-2-pyridyl)-5-(substituted amino)pyrazoles, which are unsubstituted or alkyl or haloalkyl substituted in the 3-position of the pyrazole ring; PA1 U.S. Pat. No. 4,740,232 discloses as herbicides 1-(substituted phenyl)-5-(substituted amino)pyrazole compounds, which are unsubstituted in the 3-position of the pyrazole ring; PA1 EP 398,499 discloses phenyl substituted heterocyclic compounds as insecticides and acaricides, including 1-(substituted phenyl)-5-(substituted amino)pyrazoles. PA1 U.S. Pat. No. 4,822,810 discloses 1-aryl-4-cyano-3-(sulfur substituted)-5-(alkoxyN-cinnamylideneimino)pyrazoles for the control of arthropod pests. PA1 R.sup.2 is: halogen; alkyl; haloalkyl; alkoxy; haloalkoxy; nitro; thiocyanato; unsubstituted or mono- or dialkyl substituted sulfamoyl; unsubstituted or mono- or dialkyl substituted aminocarbonyl; alkoxycarbonyl; or unsubstituted or substituted R.sup.11 S(O).sub.n, in which n is 0, 1 or 2 and R.sup.11 is alkyl, haloalkyl, cycloalkyl, halocycloalkyl, cycloalkylalkyl or halocycloalkylalkyl; and wherein the alkyl moieties are linear or branched chains of 1-4 carbon atoms, the cycloalkyl moiety contains 3 to 7 carbon atoms and the halo substitution consists of one or more halogen atoms, which are the same or different, up to full substitution of the alkyl and cycloalkyl moieties; PA1 R.sup.3, R.sup.9 and R.sup.10 are hydrogen or alkyl wherein the alkyl moieties are linear or branched chains; PA1 R.sup.4 is unsubstituted or substituted phenyl or unsubstituted or substituted pyridyl wherein the phenyl or pyridyl substitution is one or more or combinations of: hydroxy or inorganic or organic salt thereof; sulfhydryl or inorganic or organic salt thereof; halogen; cyano; nitro; alkyl; haloalkyl; alkoxy; --O--alkyl--O--; O--haloalkyl--O--; haloalkoxy; alkanoyloxy; phenoxy; trialkylsilyloxy; phenyl; alkyl-S(O).sub.n or haloalkyl-S(O).sub.n, in which n is 0, 1 or 2; NR.sup.12 R.sup.13 in which R.sup.12 and R.sup.13 are individually hydrogen, alkyl, alkanoyl or haloalkanoyl; COR.sup.14 in which R.sup.14 is NR.sup.12 R.sup.13, alkoxy, alkylthio, hydroxy or inorganic or organic salt thereof, hydrogen, alkyl or haloalkyl; or SO.sub.2 R.sup.15 in which R.sup.15 is NR.sup.12 R.sup.13, alkoxy, alkylthio, or hydroxy or inorganic or organic salt thereof; and wherein the alkyl and alkoxy moieties are linear or branched chains of 1-4 carbon atoms and the halo substitution consists of one or more halogen atoms, which are the same or different, up to full substitution of the alkyl and alkoxy moieties; PA1 R.sup.5 is hydrogen, halogen or linear or branched chain C.sub.1-4 alkyl; PA1 R.sup.6 and R.sup.8 are each individually hydrogen or fluorine; PA1 R.sup.7 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano, nitro, alkylcarbonyl, haloalkylcarbonyl, alkyl-S(O).sub.n or haloalkyl-S(O).sub.n in which n is 0, 1 or 2; and wherein the alkyl and alkoxy moieties are linear or branched chains of 1-4 carbon atoms and the halo substitution consists of one or more halogen atoms, which are the same or different, up to full substitution of the alkyl and alkoxy moieties; and PA1 X is a nitrogen atom (N) or C--R.sup.16 in which R.sup.16 is hydrogen, halogen, cyano, nitro, C.sub.1-4 alkyl, C.sub.1-4 alkylthio or C.sub.1-4 alkoxy; and the alkyl moieties are linear or branched chains. PA1 R.sup.1 is cyano, nitro or halogen; PA1 R.sup.2 is unsubstituted or substituted R.sup.11 S(O).sub.n, in which n is 0, 1 or 2 and R.sup.11 is alkyl or haloalkyl as defined; PA1 R.sup.3, R.sup.9 and R.sup.10 are hydrogen; PA1 R.sup.4 is unsubstituted or substituted phenyl or unsubstituted or substituted pyridyl; PA1 R.sup.5 is hydrogen, halogen or alkyl; PA1 R.sup.6 and R.sup.8 are each individually hydrogen or fluorine; PA1 R.sup.7 is halogen, alkyl, haloalkyl or haloalkoxy; and PA1 X is a nitrogen atom (N) or C--R.sup.16 in which R.sup.16 is hyrogen, halogen, cyano, alkyl, alkylthio or alkoxy. PA1 R.sup.4 is unsubstituted or substituted phenyl in which the substituents are one or more: hydroxy; halogen, preferably F, Cl or Br; alkoxy, preferably methoxy or ethoxy; alkylthio, preferably methylthio; cyano; or alkyl, preferably methyl or ethyl; or combinations thereof; PA1 R.sup.5 is: hydrogen; alkyl, preferably methyl; or halogen, preferably F, Cl or Br; PA1 R.sup.7 is: halogen, preferably F, Cl or Br; alkyl, preferably methyl; haloalkyl, preferably trihalomethyl and more preferably trifluoromethyl; or haloalkoxy, preferably trihalomethoxy and more preferably trifluoromethoxy; and in which halo is F, Cl or Br or combinations thereof; and PA1 X is a nitrogen atom or C--R.sup.16 in which R.sup.16 is: hydrogen; halogen, preferably F, Cl or Br; cyano; alkyl, preferably methyl or ethyl; alkylthio, preferably methylthio or ethylthio; or alkoxy, preferably methoxy or ethoxy.
It is thus apparent that the nature and position of substituent groups on a pyrazole ring provide widely different types of biological activity which type and level of activity is not readily apparent.